CN103073304B - Process for preparing ZrB2-SiC composite powder with electric melting method - Google Patents
Process for preparing ZrB2-SiC composite powder with electric melting method Download PDFInfo
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- CN103073304B CN103073304B CN201310015596.8A CN201310015596A CN103073304B CN 103073304 B CN103073304 B CN 103073304B CN 201310015596 A CN201310015596 A CN 201310015596A CN 103073304 B CN103073304 B CN 103073304B
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Abstract
The invention discloses a process for preparing ZrB2-SiC composite powder with an electric melting method. The process comprises the steps as follows: taking zirconite, boric acid and petroleum coke as initial raw materials, uniformly mixing the raw materials, milling for 1-5 h, and adding a proper amount of paper pulp waste liquor to form a similar spherical body with the diameter of 10-30 mm; drying the similar spherical body, placing into an electric arc furnace, heating to 60 DEG C, insulating for 6-12 h, heating to 120 DEG C, insulating for 6-10 h, continuing to heat to 180 DEG C, and insulating for 12-20 h; and controlling the voltage to be 80-150 V and the current to be 2000-4000 A, melting the raw materials and keeping for 5-30 min, wherein the mass ratio of zirconite, petroleum coke and boric acid is 100:(70-150):(180-250). According to the invention, the process is simple, the cost is low, the melting speed is high, the yield is high, the electric melting furnace with larger capacity can be adopted, the process is easy for industrial large-scale production, and the purity of the composite powder can reach more than 97%.
Description
Technical field
The invention belongs to technical field of inorganic nonmetallic materials, relate to the preparation method of a kind of high-performance ceramic raw material, refractory materials additive, be specifically related to a kind of ZrB
2the electric smelting method preparation technology of-SiC composite granule.
Technical background
Electric smelting legal system has for ceramic raw material that technique is simple, flow process is short, product cost is low, single pass yield advantages of higher, be commonly used to prepare the oxide ceramics raw materials such as zirconium white, corundum, zircon corundum and zircon corundum-mullite, and utilize electric smelting legal system less for the research report of non-oxidized substance.ZrB
2all there is higher fusing point with SiC, lower thermal expansivity, higher thermal conductivity and good heat-shock resistance and resistance to fouling, by ZrB
2with the compound ZrB that solves of SiC
2the problem of the poor and poor toughness of high temperature (>=1100 ℃) oxidation-resistance; Chinese patent " a kind of zirconium diboride/composite material of silicon carbide and utilize arc-melting in-situ reaction preparation method " (application number: 201210126970.7), zirconium diboride/composite material of silicon carbide is that to adopt zirconium powder, boron carbide powder and carborundum powder be raw material; under argon shield, with electric arc furnace, dried mixed powder is melted and it reacted be prepared from; but raw materials used expensive; bonding agent adopts water glass, the Na in water glass
+easily with system in other substance reaction generation low-melting-point material phase, the practical application of zirconium diboride/composite material of silicon carbide is had to negative impact, and argon shield is difficult for realizing scale operation.
Prepare at present ZrB
2the method of-SiC composite granule mostly adopts expensive raw material, as ZrO
2, norbide etc., adopt chemical method (as sol-gel method), be therefore difficult to scale operation application.
Summary of the invention
In order to solve the preparation technology of current zirconium diboride/composite material of silicon carbide, exist the problem that technical process is short, product cost is high, the object of this invention is to provide and a kind ofly adopt the relatively low raw material of price and there is a kind of ZrB that tap to tap time is short, product is pure, cost is low and be easy to scale operation
2the electric smelting method preparation technology of-SiC composite granule.
The technical solution used in the present invention realizes in the following manner:
A kind of ZrB
2the electric smelting method preparation technology of-SiC composite granule, take zircon, boric acid and refinery coke as starting raw material, and various raw materials add appropriate spent pulping liquor to be shaped to globoid after mixing mix grinding 1-5 hour, and the diameter of the globoid of preparation is 10-30mm; After globoid is dry, put into electric arc furnace, adopt reinforced method gradually; Be warming up to 60 ℃ of insulation 6-12 hour, then be warming up to 120 ℃ of insulation 6-10 hour, continue to be warming up to 180 ℃ of insulation 12-20 hour; Voltage control is at 80-150V, current control is at 2000-4000A, after various raw materials melt, maintain 5-30min, then cut off the electricity supply, promote electrode and cover carbon dust at bath surface, after furnace cooling, take out electric smelting material broken and levigate to 200 orders, and with magnet, remove the iron being reduced out; Raw materials quality ratio is: zircon: refinery coke: boric acid=100:70-150: 180-250.
The preferred technical scheme of the present invention is as follows:
Raw materials quality ratio is: zircon: refinery coke: boric acid=100:70:180, each raw material mix grinding is made globoid after 5 hours and is dried, when dry, be first warming up to 60 ℃ of insulations 6 hours, then be warming up to 120 ℃ of insulations 6 hours, continue to be warming up to 180 ℃ of insulations 12 hours; During smelting, voltage control is at 80-100V, and current control is at 2000-2500A, make the whole meltings of compound after electric arc maintain 30min.
The preferred technical scheme of the present invention is as follows:
Raw materials quality ratio is: zircon: refinery coke: boric acid=100:100:200, each raw material mix grinding is made globoid after 5 hours and is dried, when dry, be first warming up to 60 ℃ of insulations 8 hours, then be warming up to 120 ℃ of insulations 8 hours, continue to be warming up to 180 ℃ of insulations 15 hours; During smelting, voltage control is at 100-120V, and current control is at 2500-3000A, make the whole meltings of compound after electric arc maintain 20min.
The preferred technical scheme of the present invention is as follows:
Raw materials quality ratio is: zircon: refinery coke: boric acid=100:120:220, each raw material mix grinding is made globoid after 3 hours and is dried, when dry, be first warming up to 60 ℃ of insulations 8 hours, then be warming up to 120 ℃ of insulations 10 hours, continue to be warming up to 180 ℃ of insulations 18 hours; During smelting, voltage control is at 120-140V, and current control is at 3000-3500A, make the whole meltings of compound after electric arc maintain 10min.
The preferred technical scheme of the present invention is as follows:
Raw materials quality ratio is: zircon: refinery coke: boric acid=100:150:250, each raw material mix grinding is made globoid after 1 hour and is dried, when dry, be first warming up to 60 ℃ of insulations 10 hours, then be warming up to 120 ℃ of insulations 10 hours, continue to be warming up to 180 ℃ of insulations 20 hours; During smelting, voltage control is at 140-150V, and current control is at 3500-4000A, make the whole meltings of compound after electric arc maintain 5min.
?each main component quality percentage composition of described zircon is: ZrO
265 ~ 67%, SiO
230 ~ 34%, Al
2o
3≤ 0.5%, TiO
2≤ 0.5%, Fe
2o
3≤ 0.3%, Na
2o+K
2o≤0.15%, granularity is less than 0.074mm.
Described boric acid purity is greater than 99%, and granularity is less than 0.074mm.
Described refinery coke purity is greater than 97%, and granularity is less than 0.074mm.
Described various raw materials adopt ball milling to be dry mixed method, and the ball adopting in mixing step is one or more in zirconia ball, norbide ball and Stainless Steel Ball.
In the present invention, the proportioning of each material is the higher ZrB of preparation purity
2the prerequisite of-SiC composite granule, boric acid is volatile in fusion process, should be suitably excessive; Make zircon and acid reaction complete, should make refinery coke suitably excessive.In raw material mixing step, mixing time is very crucial, and the time is too short, and each mixing of materials is irregular, and reaction is just not thorough; Mixing time is long, easily produces segregations cause incomplete mixing because the density of each raw material is different, wastes energy again.Select suitable drying process can make moisture thoroughly get rid of, make again material group be unlikely loose at drying stage, thereby be conducive to carrying out smoothly of smelting.Smelting voltage and current control is the key process parameter of preparation, and voltage is slow compared with low reaction speed, production efficiency is low, and overtension makes new synthetic ZrB
2thereby-SiC composite granule partial oxidation makes purity drop.The weight percent of composite granule shows its purity, and purity is higher, and the quality of composite granule is better.
Positively effect of the present invention is:
1, the invention provides and take cheap zircon, refinery coke and boric acid and prepare high added value ZrB as raw material adopts electric smelting technique
2-SiC composite granule, has that technique is simple, cost is low, burn-off rate fast (short flow process), and productive rate is high, can adopt the electric smelter that volume is larger, is easy to large-scale industrialization and produces.
2, reaction mechanism of the present invention is different from the solid state reaction in other preparation method, and each material is fused into very soon liquid state under the effect of electric arc, belongs to liquid phase reaction, and each storeroom mass transfer velocity is fast, short and sufficient reacting of reaction times.
3, the composite granule purity that prepared by the present invention is high, and while adopting electric smelting method, potassium, sodium and compound thereof are overflowed with volatile matter in electric smelting process, and composite granule purity is more than 97%.
4, the prepared ZrB of the present invention
2the iron being reduced out in-SiC composite granule can be removed by magnet, trace impurity phase TiO
2can be converted into high-melting-point, high-performance ceramic phase TiC or TiB
2, trace impurity phase Al
2o
3fusing point is very high, and by product is the B of high-melting-point, excellent property
4c, the powder industryization application that the existence of these phases is prepared the present invention is without negative impact.
5, ZrB provided by the present invention
2the standby New methods in working that provides of electric smelting legal system that the electric smelting method preparation technology of-SiC composite granule is non-oxidized substance composite granule.
Accompanying drawing explanation:
Fig. 1 is the standby ZrB of electric smelting legal system
2the thing phase composite figure of-SiC composite granule.
Fig. 2 is the standby ZrB of electric smelting legal system
2the micro-structure diagram of-SiC composite granule.
Embodiment
Below in conjunction with embodiment, the invention will be further described, but be not limited to the following example.
Zircon: refinery coke: boric acid=100:70:180(mass ratio), with zirconia ball mix grinding, mix 5 hours; After mixing, material be take spent pulping liquor and is made as bonding agent the globoid that diameter is 10mm, is then dried, and is first warming up to 60 ℃ of insulations 6 hours, then is warming up to 120 ℃ of insulations 6 hours, continues to be warming up to 180 ℃ of insulations 12 hours; Dried globoid is put into electric arc furnace in batches; Adopt submerged arc method to smelt, voltage control is at 80-100V, and current control is at 2000-2500A, make the whole meltings of compound after electric arc maintain 30min, then cut off the electricity supply, promote electrode, and cover bath surface with carbon dust; Cool to the furnace after room temperature, take out electric smelting material, after fragmentation, be finely ground to granularity <200 object composite granule, and with magnet, remove the iron being reduced out.
Zircon: refinery coke: boric acid=100:100:200(mass ratio), with norbide ball mix grinding, mix 5 hours; After mixing, material be take spent pulping liquor and is made as bonding agent the globoid that diameter is 20mm, is then dried, and is first warming up to 60 ℃ of insulations 8 hours, then is warming up to 120 ℃ of insulations 8 hours, continues to be warming up to 180 ℃ of insulations 15 hours; Dried globoid is put into electric arc furnace in batches; Adopt submerged arc method to smelt, voltage control is at 100-120V, and current control is at 2500-3000A, make the whole meltings of compound after electric arc maintain 20min, then cut off the electricity supply, promote electrode, and cover bath surface with carbon dust; Cool to the furnace after room temperature, take out electric smelting material, after fragmentation, be finely ground to granularity <200 object composite granule, and with magnet, remove the iron being reduced out.
Zircon: refinery coke: boric acid=100:120:220(mass ratio), with Stainless Steel Ball mix grinding, mix 3 hours; After mixing, material be take spent pulping liquor and is made as bonding agent the globoid that diameter is 30mm, is then dried, and is first warming up to 60 ℃ of insulations 8 hours, then is warming up to 120 ℃ of insulations 10 hours, continues to be warming up to 180 ℃ of insulations 18 hours; Dried globoid is put into electric arc furnace in batches; Adopt submerged arc method to smelt, voltage control is at 120-140V, and current control is at 3000-3500A, make the whole meltings of compound after electric arc maintain 10min, then cut off the electricity supply, promote electrode, and cover bath surface with carbon dust; Cool to the furnace after room temperature, take out electric smelting material, after fragmentation, be finely ground to granularity <200 object composite granule, and with magnet, remove the iron being reduced out.
Embodiment 4
Zircon: refinery coke: boric acid=100:150:250(mass ratio), with zirconia ball and norbide ball mix grinding, mix 1 hour; After mixing, material be take spent pulping liquor and is made as bonding agent the globoid that diameter is 30mm, is then dried, and is first warming up to 60 ℃ of insulations 10 hours, then is warming up to 120 ℃ of insulations 10 hours, continues to be warming up to 180 ℃ of insulations 20 hours; Dried globoid is put into electric arc furnace in batches; Adopt submerged arc method to smelt, voltage control is at 140-150V, and current control is at 3500-4000A, make the whole meltings of compound after electric arc maintain 5min, then cut off the electricity supply, promote electrode, and cover bath surface with carbon dust; Cool to the furnace after room temperature, take out electric smelting material, after fragmentation, be finely ground to granularity <200 object composite granule, and with magnet, remove the iron being reduced out.
The ZrB that electric smelting technique is prepared
2thing phase composite and the microstructure of-SiC composite granule are shown in accompanying drawing 1 and Fig. 2.
As shown in Figure 1, the thing phase composite of composite granule is mainly ZrB
2-SiC, also has a small amount of high-melting-point phase B
4c; Utilize the integral area of each thing phase diffraction peak in Fig. 1 can calculate the relative content of each thing phase.
By Fig. 2, known ZrB
2particle diameter is larger, and it is tiny granular that SiC is, and the disperse of SiC crystal is at ZrB
2in skeleton structure.
Claims (9)
1. a ZrB
2the electric smelting method preparation technology of-SiC composite granule, take zircon, boric acid and refinery coke as starting raw material, and various raw materials add appropriate spent pulping liquor to be shaped to globoid after mixing mix grinding 1-5 hour, and the diameter of the globoid of preparation is 10-30mm; After globoid is dry, put into electric arc furnace, adopt reinforced method gradually; Heating mode when globoid is dry: be warming up to 60 ℃ of insulation 6-12 hour, then be warming up to 120 ℃ of insulation 6-10 hour, continue to be warming up to 180 ℃ of insulation 12-20 hour; The voltage control of dried globoid in electric arc furnace is at 80-150V, current control is at 2000-4000A, after various raw materials melt, maintain 5-30min, then cut off the electricity supply, promote electrode and cover carbon dust at bath surface, after furnace cooling, take out electric smelting material broken and levigate to 200 orders, and with magnet, remove the iron being reduced out; Raw materials quality ratio is: zircon: refinery coke: boric acid=100:70-150: 180-250.
2. a kind of ZrB according to claim 1
2the electric smelting method preparation technology of-SiC composite granule, it is characterized in that: raw materials quality ratio is: zircon: refinery coke: boric acid=100:70:180, each raw material mix grinding is made globoid after 5 hours and is dried, when dry, be first warming up to 60 ℃ of insulations 6 hours, be warming up to again 120 ℃ of insulations 6 hours, continue to be warming up to 180 ℃ of insulations 12 hours; During smelting, voltage control is at 80-100V, and current control is at 2000-2500A, make the whole meltings of compound after electric arc maintain 30min.
3. a kind of ZrB according to claim 1
2the electric smelting method preparation technology of-SiC composite granule, it is characterized in that: raw materials quality ratio is: zircon: refinery coke: boric acid=100:100:200, each raw material mix grinding is made globoid after 5 hours and is dried, when dry, be first warming up to 60 ℃ of insulations 8 hours, be warming up to again 120 ℃ of insulations 8 hours, continue to be warming up to 180 ℃ of insulations 15 hours; During smelting, voltage control is at 100-120V, and current control is at 2500-3000A, make the whole meltings of compound after electric arc maintain 20min.
4. a kind of ZrB according to claim 1
2the electric smelting method preparation technology of-SiC composite granule, it is characterized in that: raw materials quality ratio is: zircon: refinery coke: boric acid=100:120:220, each raw material mix grinding is made globoid after 3 hours and is dried, when dry, be first warming up to 60 ℃ of insulations 8 hours, be warming up to again 120 ℃ of insulations 10 hours, continue to be warming up to 180 ℃ of insulations 18 hours; During smelting, voltage control is at 120-140V, and current control is at 3000-3500A, make the whole meltings of compound after electric arc maintain 10min.
5. ZrB according to claim 1
2the electric smelting method preparation technology of-SiC composite granule, it is characterized in that: raw materials quality ratio is: zircon: refinery coke: boric acid=100:150:250, each raw material mix grinding is made globoid after 1 hour and is dried, when dry, be first warming up to 60 ℃ of insulations 10 hours, be warming up to again 120 ℃ of insulations 10 hours, continue to be warming up to 180 ℃ of insulations 20 hours; During smelting, voltage control is at 140-150V, and current control is at 3500-4000A, make the whole meltings of compound after electric arc maintain 5min.
6. according to a kind of ZrB described in claim 1,2,3,4 or 5
2the electric smelting method preparation technology of-SiC composite granule, is characterized in that: each main component quality percentage composition of zircon is: ZrO
265 ~ 67%, SiO
230 ~ 34%, Al
2o
3≤ 0.5%, TiO
2≤ 0.5%, Fe
2o
3≤ 0.3%, Na
2o+K
2o≤0.15%, granularity is less than 0.074mm.
7. a kind of ZrB according to claim 6
2the electric smelting method preparation technology of-SiC composite granule, is characterized in that: described boric acid purity is greater than 99%, and granularity is less than 0.074mm.
8. a kind of ZrB according to claim 7
2the electric smelting method preparation technology of-SiC composite granule, is characterized in that: described refinery coke purity is greater than 97%, and granularity is less than 0.074mm.
9. a kind of ZrB according to claim 6
2the electric smelting method preparation technology of-SiC composite granule, is characterized in that: described various raw materials adopt ball milling to be dry mixed method, and the ball adopting in mixing step is one or more in zirconia ball, norbide ball and Stainless Steel Ball.
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| CN103449463B (en) * | 2013-09-12 | 2015-09-16 | 武汉科技大学 | A kind of Zirconium boride-silicon carbide composite powder and preparation method thereof |
| CN106316402A (en) * | 2016-08-09 | 2017-01-11 | 山东大学 | ZrB2/SiC composite powder special for thermal spraying ceramic coating and preparation method of ZrB2/SiC composite powder |
| CN106495715B (en) * | 2016-10-26 | 2019-10-25 | 马鞍山利尔开元新材料有限公司 | A kind of ZrB2Nozzle brick and preparation method thereof outside-SiC powder modified converter slag-resisting slide gate nozzle |
| CN110627508A (en) * | 2019-08-28 | 2019-12-31 | 广东工业大学 | High-entropy boride-based ceramic and preparation method and application thereof |
| CN113121225A (en) * | 2021-04-23 | 2021-07-16 | 中钢集团洛阳耐火材料研究院有限公司 | Anti-sintering YTaO4Method for preparing ceramic powder |
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| JPH11278940A (en) * | 1998-03-27 | 1999-10-12 | Kurosaki Refract Co Ltd | Alumina-silicon carbide refractory |
| JP4163783B2 (en) * | 1998-03-27 | 2008-10-08 | 黒崎播磨株式会社 | Alumina-silicon carbide refractories |
| CN102320850B (en) * | 2011-09-02 | 2013-05-08 | 郑州大学 | ZrB2-SiC composite powder and preparation method thereof |
| CN102633504A (en) * | 2012-04-26 | 2012-08-15 | 天津大学 | Zirconium diboride/silicon carbide composite material and method for preparing same by means of arc melting in-suit reaction |
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